429503 Charge Transport and Structural Dynamics in Polymerized Ionic Liquids

Monday, November 9, 2015: 3:15 PM
251E (Salt Palace Convention Center)
Joshua Sangoro, Chemical and Biomolecular Engineering, University of Tennessee, Knoxville, TN

Polymerized ionic liquids (PolyILs) are a novel class of functional polymers that combine the unique physicochemical properties of molecular ionic liquids with the outstanding mechanical characteristics of polymers [1-2]. This special mix of features might help to circumvent the key limitations of low molecular weight ionic liquids, namely, leakage and poor mechanical properties while utilizing their outstanding characteristics such as low vapor pressures, wide liquidus ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. PolyILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices, among others. Despite their promising prospects as ideal polymer electrolytes, the role of molecular structure, morphology, and polymer dynamics on charge transport in PolyILs remains poorly understood. According to classical theories, the self-diffusion and ion transport in electrolytes are controlled by structural relaxation. These approaches predict similar temperature dependence for the dc conductivity and structural dynamics. Although this prediction has been shown to hold reasonably well for low molecular weight aprotic ionic liquids [3], it fails for PolyILs [2]. In addition, the impact of morphology charge transport is not considered within the framework of these theories.

            In this talk, new insights obtained from experimental studies employing broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, and scattering techniques to elucidate charge transport and structural dynamics in a systematic series of polymerized ammonium- and imidazolium- based ionic liquids will be presented. Detailed analyses reveal strong decoupling of these processes in the PolyILs, implying failure of the classical theories in describing charge transport and molecular dynamics in these materials. The strong correlation observed between ionic conductivity from dielectric experiments and morphologies from scattering studies will be discussed. The potential of tuning the molecular parameters to increase the ionic conductivity of polymerized ionic liquids will be discussed as well.

References

1)      Mecerreyes, D. Progress in Polymer Science 2011, 36, 1629.

2)      Sangoro, J. R. et al., Soft Matter 2014, 10, 3536.

3)      Sangoro, J. R.; Kremer, F. Accounts of Chemical Research 2012, 45, 525.

4)      J. R. Sangoro, C. Iacob, A. Serghei, C. Friedrich, F. Kremer, Phys. Chem. Chem. Phys. 2009, 11, 913.


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See more of this Session: Charged and Ion-Containing Polymers
See more of this Group/Topical: Materials Engineering and Sciences Division